CN1575272A - Method for preparing 4-nitroso-substituted aromatic amine - Google Patents
Method for preparing 4-nitroso-substituted aromatic amine Download PDFInfo
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- CN1575272A CN1575272A CNA02820865XA CN02820865A CN1575272A CN 1575272 A CN1575272 A CN 1575272A CN A02820865X A CNA02820865X A CN A02820865XA CN 02820865 A CN02820865 A CN 02820865A CN 1575272 A CN1575272 A CN 1575272A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/08—Preparation of carboxylic acid amides from amides by reaction at nitrogen atoms of carboxamide groups
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Abstract
Disclosed is a method for preparing a 4-nitroso-substituted aromatic amine that includes contacting an amide compound with a nitroaromatic compound in the presence of a base and a solvent to directly prepare 4-nitroso-substituted aromatic amine as a main product and 4-nitro-substituted aromatic amine as a by-product without producing 4-nitroso- or 4-nitro-substituted amide as an intermediate.
Description
Technical field
The present invention relates to a kind of method of aromatic amine of the 4-of preparation nitroso-group replacement, more specifically, relate in the polar organic solvent in the presence of alkali, optionally prepare the method for the aromatic amine of 4-nitroso-group replacement by amide compound is contacted with nitroaromatic.
Technical background
Usually, the aromatic amine that replaces as the 4-nitroso-group of the intermediate of dyestuff or hair dye and light stabilizer partly, because the preparation method of their complexity, the research that their are used also is not a lot.In the aromatic amine that the 4-nitroso-group replaces, the 4-nitrosoaniline is used as the intermediate of dyestuff or hair dye, and usually is reduced to the raw material (USP 6,245,943) of preparation p-phenylenediamine.
Routinely, the 4-nitrosoaniline is by making aniline and Sodium Nitrite (NaNO
2) contact generates the N-nitrosoaniline, then under acidic conditions the N-nitrosoaniline carry out that Fischer-Hepp resets and preparation (Tetrahedron, 1975,31,1343-9), or-nitrosophenol right and ammonia or ammonium chloride (NH by making
4Cl) contact (USP 3,338, and 966; And J.Chem.Soc., 1955,2049) and preparation.
Preceding a kind of method is included in the nitrosylation that takes off in the nitrosamine rearrangement step, generates the refuse that contains many environmentally harmful nitroso compounds.There is the low-down problem of productive rate of 4-nitrosoaniline in the method for a kind of 4-of the employing nitrosophenol in back, and this problem causes the difficulty of 4-nitrosoaniline scale operation, and has therefore limited the use of 4-nitrosoaniline.
Recently, developed that a kind of nucleophilic aromatic by hydrogen replaces (NASH) and selectivity prepares the method for N-methyl-p-nitroaniline.For example, at organic bases, tetramethylammonium hydroxide (below be called " TMA (OH) ") exists down, benzamide or benzonitrile contact with oil of mirbane, generate intermediate N (4-nitrophenyl) benzamide, then it is isolated and decompose and generate 4-N-methyl-p-nitroaniline and M-nitro benzoic acid (or benzamide) (J.Org.Chem, 1993 by adding water (perhaps ammonia), 58 (24), 6883-8; USP 5,436, and 371 and 5,331,099; With WO 93/24447).This method is a kind of use NASH, and directly amination oil of mirbane prepares the 4-N-methyl-p-nitroaniline with two-step approach, is also referred to as the method for " p-Nitraniline ".
Another kind of also is that known (EP 695739 by the similarity method that uses NASH to react the nitroaromatic that direct amination preparation replaces; With JP 8040994).
In addition, another kind of known method comprises makes fatty amide, and isobutyramide contacts with benzene, generates intermediate N (4-nitrophenyl) butyramide (USP5,331,099).In the method, N-(4-nitrophenyl) butyramide and ammonia decompose or the generation 4-N-methyl-p-nitroaniline that is hydrolyzed.
Well-known, use the NASH reaction, the direct amination of amide compound and nitroaromatic generates the intermediate of the aromatic amine of 4-nitro replacement, and this intermediate and water or ammonia resolve into the aromatic amine that the 4-nitro replaces.But, do not prepare the pertinent literature of the aromatic amine that the 4-nitroso-group replaces.
But the aromatic amine that 4-nitroso-group or 4-nitro replace can also be made by direct amination, and described direct amination comprises that the aniline rather than the amide compound that make as a kind of aromatic amine contact with oil of mirbane, carry out NASH reaction (J.Am.Chem.Soc., 1992,114 (23), 9237-8; With USP 5,117,063).
As above statement comprises that the traditional method of reacting between amide compound and the oil of mirbane is a kind of two-stage process, and the first step generates the intermediate of the aromatic amides of 4-nitro replacement, and intermediate and ammonia or water are hydrolyzed into the aromatic amine that the finished product 4-nitro replaces then.In the method, the method for the aromatic amine of preparation 4-nitroso-group replacement is unknown.
Summary of the invention
Therefore, the present inventor has studied a kind of use NASH reaction, under suitable condition, do not generate the one step process of the acid amides of intermediate 4-nitroso-group or the replacement of 4-nitro by the aromatic amine of amide compound and the replacement of nitroaromatic prepared in reaction 4-nitroso-group.
Therefore, an object of the present invention is to provide a kind ofly in the presence of alkali, make nitroaromatic contact the method with highly selective and high yield of the aromatic amine that aromatic amine that a step preparation 4-nitroso-group replaces and 4-nitro replace with amide compound.
In order to reach purpose of the present invention, a kind of method of aromatic amine of the 4-of preparation nitroso-group replacement is provided, this method is included in alkali and exists down, the nitroaromatic of following formula 3 expression and the amide compound of following formula 4 expressions contacts, directly prepare the aromatic amine that the major product 4-nitroso-group of following formula 1 expression replaces and the aromatic amine of byproduct 4-nitro replacement with single stage method:
Formula 1
Wherein, Ar is for having one or at least one ring and comprising one or two N, the heteroatomic C of O or S
4To C
16Aromatic base; X is a halogen atom, cyano group, C
1To C
4Alkyl, halogenated C
1To C
4Alkyl, C
1To C
4Alkoxyl group, C
1To C
4Halogenated alkoxy, C
1To C
4Alkyl sulphonyl, or C
1To C
4The alkyl nitro; And n is 0 to 3 integer, wherein when n greater than 1 the time, X is differing from each other;
Formula 2
Ar wherein, X and n are as defined above;
Formula 3
Ar wherein, X and n are as defined above; With
Formula 4
Wherein R is a hydrogen atom, C
1To C
8Alkyl, C
2To C
8Alkenyl, or C
3To C
7Cycloalkyl, its substituting group can be with 1 to 3 halogen atom, C
1To C
4Alkyl, amino or C
1To C
4Alkoxyl group replaces.
The aromatic amine that 4-nitroso-group that obtains thus and 4-nitro replace carries out normal hydrogenation reaction easily and generates the diamines substituted aromatics.
The present invention aims to provide in a kind of polar organic solvent in the presence of inorganic or organic bases, is prepared the method for the aromatic amine of 4-nitroso-group replacement with very high selectivity by amide compound and nitroaromatic.
In preparation method of the present invention, the aromatic amine that the nitroso-group of being made by the amide compound of the nitroaromatic of formula 3 and formula 4 replaces is by formula 1 expression, and generates the aromatic amine (formula 2) that a small amount of nitro replaces simultaneously.Oxygen and air atmosphere can suppress the generation of byproduct zinin, and therefore can optionally prepare the aromatic amine that nitroso-group replaces.
More specifically, the example of nitroaromatic that is suitable as the formula 3 of raw material can comprise oil of mirbane, the 3-nitroanisole, and the 3-nitrotoluene, the 2-nitroanisole, the 2-nitrotoluene ,-chloronitrobenzene, 2,3,4-nitropyridine and 5,6,7-nitroquinoline.
The specific examples of the amide compound of the formula 4 that contacts with nitroaromatic can comprise urea, ethanamide, methane amide, biuret, phenylurea and isobutyramide.
Be applicable to that alkali of the present invention comprises mineral alkali and organic bases.The specific examples of mineral alkali can comprise alkali metal hydroxide, alkali amide (alkali metal amides), alkali metal alcoholates, and alkalimetal hydride.In these mineral alkalis, preferred alkali metal hydroxide is sodium hydroxide (NaOH), and potassium hydroxide (KOH), and potassium tert.-butoxide (t-BuOK) are preferably powder or fine particulate form.
The specific examples of organic bases can comprise tetra-alkyl ammonium hydroxide, and preferred especially TMA (OH).
The use of phase-transfer catalyst and mineral alkali can improve reactivity.The specific examples of phase-transfer catalyst can comprise crown ether and tetraalkyl ammonium salt.In these catalyzer, particularly preferably be hexaoxacyclooctadecane-6-6 and tetramethylammonium chloride (below be called " TMA (Cl) ").
The mol ratio of the amide compound of alkali and formula 4 is 1: 0.5 to 1: 10, is preferably 1: 1 to 1: 6.
The specific examples of solvent can comprise polar organic solvent, dimethyl sulfoxide (DMSO) (below be called " DMSO ") for example, dimethyl formamide (below be called " DMF "), N-Methyl pyrrolidone (below be called " NMP "), pyridine ， diox, and tetrahydrofuran (THF) (below be called " THF ").These solvents can use separately or be used in combination.In these solvents, DMSO most preferably.Alternatively, amide compound or nitroaromatic itself can be used as solvent.
The weight ratio of the amide compound of solvent and formula 4 is 1: 0.5 to 1: 50, is preferably 1: 1 to 1: 20.
In order to improve the selectivity of the aromatic amine that product 4-nitroso-group of the present invention replaces, time of pre-fixed length to as slowly adding nitroaromatic in the amide compound of raw material.
The mol ratio of the nitroaromatic of the amide compound of formula 4 and formula 3 is 1: 1 to 1: 30, is preferably 1: 1.5 to 1: 6.The ratio of higher amide compound has improved the selectivity of the aromatic amine of 4-nitroso-group replacement, and the ratio of higher nitroaromatic has not only increased the ratio of the aromatic amine that the 4-nitro replaces but also has caused generating the side reaction product, byproduct 4,4 '-dinitro diphenylamine.Therefore the amount of the amide compound of preferred formula 4 is in above-mentioned scope.
The use of vacuum distilling or siccative can be used for removing the water early stage or that generated by reaction soln in reaction in reaction process.The specific examples that is applicable to siccative of the present invention can comprise Anhydrous potassium carbonate, anhydrous sodium sulphate, anhydrous magnesium sulfate, sodium hydroxide, potassium hydroxide, sodium hydride, and molecular sieve.But in preparation method of the present invention, the quantity of water influences reaction hardly, and the water that therefore uses siccative or continuous still battery to remove in the solution only causes seldom difference to the productive rate of product.
Suitable temperature of reaction is 20 to 150 ℃, is preferably 70 to 100 ℃.Be lower than the selectivity that 20 ℃ temperature of reaction has reduced speed of response and reduced the aromatic amine that the 4-nitroso-group replaces, increased the output of byproduct and be higher than 150 ℃ temperature of reaction, thereby the productive rate of product worsened.
Nitrogen, oxygen or air can be used as reaction atmosphere of the present invention.Nitrogen atmosphere causes the generation of byproduct zinin, and oxygen or air atmosphere have suppressed the generation of zinin and improved product yield.
In the present invention, product adopts nucleus magnetic resonance and gas chromatography-mass spectrum calibrating method of masurement analysis and discriminating, and reactant and product adopt under high performance liquid chromatography (below be called " the HPLC ") condition below and carry out quantitative analysis.As for HPLC, use a kind of Hitachi's product of forming by L-6200 intelligent pump and L-4200 ultraviolet-visible spectrum detector for measuring, measure under 254nm with Cosmosil 5C18 (4.6 * 150mm, packed column), the development rate of chromatographic eluents is 1ml/min.The condition of solvent gradient elution is listed in table 1.
Table 1
| The solvent gradient elution rate | ||
| Solvent orange 2 A | Solvent B | |
| Time (min) | Purify waste water % | Acetonitrile, % |
| ????0 | ????85 | ????15 |
| ????25 | ????0 | ????100 |
| ????33 | ????85 | ????15 |
Pyrene is a kind of internal standard substance as products measure, and the concentration of measuring every kind of raw material as standard calibration based on the pyrene area area ratio, thereby with the volumetric molar concentration of calibration curve counting yield.
Implement best mode of the present invention
Below, will describe the present invention in detail by the following examples, these embodiment also are not intended to limit the scope of the invention.
Embodiment 1
Ethanamide with 2.0g (34 mmole), the potassium hydroxide of (4.1g 68 mmole), the 10g Anhydrous potassium carbonate, the DMSO of 200mg pyrene and 15ml joins in the reactor of the 100ml that is equipped with condenser and thermometer, and in oxygen atmosphere the stirring heating mixture.When temperature of reaction reaches 85 ℃, drip about 10 minutes of the oil of mirbane of 1.4g (11 mmole) by dropping funnel.Adopt limiting alarm (extreme caution) in order to avoid the temperature in the reactor may be above 85 ± 4 ℃.The terminal point that the time point that uses HPLC that oil of mirbane is disappeared is defined as reacting.React after 2 hours, DMSO is joined in the reactant of predetermined amount,, analyze with HPLC then with the ethyl acetate dilution.
The transformation efficiency of oil of mirbane is 100%.According to quantitative analysis,, be 61 moles of % and be 8 moles of % for the 4-N-methyl-p-nitroaniline for the 4-nitrosoaniline based on the product yield of internal standard substance pyrene.
1H-NMR ([D
6] DMSO, 130 ℃): the 4-nitrosoaniline: 13.30 (s, 2H), 6.77 (d, 2H, J=8.4Hz), 7.61 (d, 2H, J=8.4Hz) (at room temperature all signals are obvious).
M/z (matrix: glycerol, ionic species: FAB
+): [M+1]
+=123.06
Comparative example 1
According to being disclosed in USP5,331,099 method is carried out this test to determine product.Opposite with result of the present invention, product is confirmed as a kind of acid amides.
More specifically, alkali TMA (OH) 5H of 1.8g (14 mmole)
2O, the benzamide of 1.2g (10 mmole) and the dimethylbenzene of 10ml carry out vacuum distilling under 740mmHg/70 ℃, stir down at 70 ℃ simultaneously, so that remove from alkali with the water in the dimethylbenzene distillation alkali and with it.Drip the oil of mirbane of 1.2g (10 mmole) then.React after 4 hours, N-(4-nitrophenyl) benzamide that the HPLC analysis revealed obtains is 98% based on the productive rate of benzamide.
Embodiment 2
The result of different acid amides is used in the present embodiment explanation.Operate with embodiment 1 described identical method, difference is to use as the listed various acid amides of table 2 and replaces ethanamide.The results are shown in table 2.
Table 2
| Acid amides | Transformation efficiency (%) | Productive rate (mole %) | |||
| Oil of mirbane | The 4-nitrosoaniline | The 4-N-methyl-p-nitroaniline | N-(4-nitrophenyl) acid amides | Other | |
| Ethanamide | ??100 | ???61 | ????8 | ????- | ???＜1 |
| Methane amide | ??84 | ???45 | ????7 | ????- | ???3 |
| Biuret | ??97 | ???43 | ????10 | ????- | ???3 |
| Benzamide | ??100 | ???- | ????- | 98 (productive rates of N-(4-nitrophenyl) benzamide) | ???2 |
Embodiment 3
Operate with embodiment 1 described identical method, difference is that listed as table 3 based on the addition of the oil of mirbane of ethanamide is variable.The results are shown in table 3.
Table 3
| Oil of mirbane/ethanamide (mol ratio) | Transformation efficiency (%) | Productive rate (mole %) | ||
| Oil of mirbane | The 4-nitrosoaniline | The 4-N-methyl-p-nitroaniline | Other | |
| ????1/3 | ???100 | ????61 | ?????8 | ????＜1 |
| ????1/2 | ???99 | ????49 | ?????14 | ????11 |
| ????1 | ???97 | ????28 | ?????9 | ????7 |
Embodiment 4
Operate with embodiment 1 described identical method, difference be the type of alkali listed as table 4 be variable.The results are shown in table 4.
Table 4
| Alkali | Transformation efficiency (%) | Productive rate (mole %) | ||
| Oil of mirbane | The 4-nitrosoaniline | The 4-N-methyl-p-nitroaniline | Other | |
| ?KOH | ????100 | ????61 | ????8 | ???＜1 |
| ?TMA(OH)·5H 2O | ????100 | ????63 | ????6 | ???＜1 |
| ?NaOH | ????98 | ????24 | ????8 | ????6 |
| ?t-BuOK | ????99 | ????15 | ????7 | ????8 |
Embodiment 5
The test of the variation of temperature of reaction is depended in the variation that present embodiment relates to a definite product yield.Operate with embodiment 1 described identical method, difference be temperature of reaction listed as table 5 be variable.The results are shown in table 5.
Table 5
| Temperature of reaction (℃) | Transformation efficiency (%) | Productive rate (mole %) | ||
| Oil of mirbane | The 4-nitrosoaniline | The 4-N-methyl-p-nitroaniline | Zinin | |
| ????50 | ????57 | ????19 | ????7 | ????- |
| ????70 | ????99 | ????58 | ????11 | ????- |
| ????85 | ????100 | ????61 | ????8 | ????- |
| ????100 | ????100 | ????35 | ????1 | ????2 |
Embodiment 6
Operate with embodiment 1 described identical method, difference be the type of solvent listed as table 6 be variable.The results are shown in table 6.
Table 6
| Solvent | Transformation efficiency (%) | Productive rate (mole %) | ||
| Oil of mirbane | The 4-nitrosoaniline | The 4-N-methyl-p-nitroaniline | Other | |
| ????DMSO | ????100 | ????61 | ????8 | ????＜1 |
| ????NMP | ????95 | ????6 | ????- | ????- |
Embodiment 7
Operate with embodiment 1 described identical method, difference is that reaction system is to be in nitrogen or the air atmosphere, the results are shown in table 7.
Table 7
| Gas | Transformation efficiency (%) | Productive rate (mole %) | ||
| Oil of mirbane | The 4-nitrosoaniline | The 4-N-methyl-p-nitroaniline | Zinin | |
| ????O 2 | ????100 | ????61 | ????8 | ????- |
| ????N 2 | ????100 | ????55 | ????7 | ????4 |
Embodiment 8
Ethanamide with 2.0g (34 mmole), the potassium hydroxide of (4.1g 68 mmole), the 10g Anhydrous potassium carbonate, the DMSO of 200mg pyrene and 15ml joins in the reactor of the 100ml that is equipped with condenser and thermometer, and in oxygen atmosphere the stirring heating mixture.When temperature of reaction reaches 85 ℃, the 3-nitrotoluene of 1.5g (11 mmole) is added drop-wise in the mixture about 10 minutes by dropping funnel.Adopt limiting alarm in order to avoid the temperature in the reactor may be above 85 ± 4 ℃.
React after 2 hours, carry out aftertreatment according to embodiment 1 is described.According to quantitative analysis, the transformation efficiency of 3-nitrotoluene is 75%, and single plant product based on the 3-nitrotoluene productive rate, be 46 moles of % and be 5 moles of % (the HPCL correction value of 2-methyl-4-nitrosoaniline is the correction value of 4-nitrosoaniline) for 2-methyl-4-nitrosoaniline for 2-methyl-4-N-methyl-p-nitroaniline.
Embodiment 9
Ethanamide with 2.0g (34 mmole), the potassium hydroxide of (4.1g 68 mmole), the 10g Anhydrous potassium carbonate, the DMSO of 200mg pyrene and 15ml joins in the reactor of the 100ml that is equipped with condenser and thermometer, and in oxygen atmosphere the stirring heating mixture.When temperature of reaction reaches 85 ℃, the 3-nitroanisole of 1.7g (11 mmole) is added drop-wise in the mixture about 10 minutes by dropping funnel.Adopt limiting alarm in order to avoid the temperature in the reactor may be above 85 ± 4 ℃.
React after 2 hours, carry out aftertreatment according to embodiment 1 is described.According to quantitative analysis, the transformation efficiency of 3-nitroanisole is 100% and based on the 3-nitroanisole, and the productive rate of various products is 29 moles of % for 2-methoxyl group-4-nitrosoaniline and is 14 moles of % (the HPCL correction value of 2-methoxyl group-4-nitrosoaniline is the correction value of 4-nitrosoaniline) for 2-methoxyl group-4-N-methyl-p-nitroaniline.
Industrial usability
As mentioned above, comprise that amide compound and nitroaromatic contact under suitable condition and do not have intermediate to generate, the preparation method that one step generated the aromatic amine that the 4-nitroso replaces is preferred economically, because it has significantly improved practicality and provides a kind of direct preparation as the intermediate of dyestuff and hair dye and be reduced to the method for the aromatic amine that the major product 4-nitroso of p-phenylenediamine (PPD) replaces.
Claims (10)
1. method for preparing the aromatic amine that the 4-nitroso-group replaces, described method comprises:
In the presence of alkali and solvent, the nitroaromatic of following formula 3 expression and the amide compound of following formula 4 expressions contacts, directly prepare the aromatic amine of the byproduct 4-nitro replacement of aromatic amine that the major product 4-nitroso-group of following formula 1 expression replaces and following formula 2 expressions with single stage method:
Formula 1
Wherein, Ar is for having at least one ring and comprise one or two N, the heteroatomic C of O or S
4To C
16Aromatic base; X is a halogen atom, cyano group, C
1To C
4Alkyl, halogenated C
1To C
4Alkyl, C
1To C
4Alkoxyl group, C
1To C
4Halogenated alkoxy, C
1To C
4Alkyl sulphonyl, or C
1To C
4The alkyl nitro; And n is 0 to 3 integer, wherein when n greater than 1 the time, X are differing from each other;
Formula 2
Ar wherein, X and n as above define;
Formula 3
Ar wherein, X and n as above define; With
Formula 4
Wherein R is a hydrogen atom, C
1To C
8Alkyl, C
2To C
8Alkenyl, or C
3To C
7Cycloalkyl, its substituting group can be with 1 to 3 halogen atom, C
1To C
4Alkyl, amino or C
1To C
4Alkoxyl group replaces.
2. method according to claim 1, the nitroaromatic of wherein said formula 3 comprise and are selected from oil of mirbane, 2-nitrotoluene, 2-nitroanisole, at least a in 3-nitrotoluene and the 3-nitroanisole.
3. method according to claim 1, the amide compound of wherein said formula 4 comprise and be selected from methane amide, at least a in ethanamide and the biuret.
4. method according to claim 1, wherein said reaction are to carry out under 50 to 120 ℃ temperature.
5. method according to claim 1, wherein said solvent comprise independent dimethyl sulfoxide (DMSO) (DMSO) or N-Methyl pyrrolidone (NMP), or the mixed solvent of DMSO and organic solvent.
6. method according to claim 1, wherein said alkali comprises sodium hydroxide, sodium hydride for being selected from, any in the basic metal of potassium hydroxide and potassium tert.-butoxide, or be selected from the mineral alkali that is used in combination with phase-transfer catalyst, and organic bases, tetramethylammonium hydroxide.
7. method according to claim 6, the wherein said phase-transfer catalyst that is used in combination with mineral alkali comprises tetramethylammonium chloride or hexaoxacyclooctadecane-6-6.
8. method according to claim 1 wherein based on the amide compound of formula 4, is used described alkali with 0.5 to 10 mol ratio.
9. method according to claim 1, the mol ratio of the nitroaromatic of the amide compound of wherein said formula 4 and formula 3 is 1: 1 to 1: 30.
10. method according to claim 1, wherein said being reflected at is selected from nitrogen, carries out in the reaction atmosphere of oxygen and air.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020010067382A KR20030035343A (en) | 2001-10-31 | 2001-10-31 | Process for the preparation of nitroso-substituted arylamines |
| KR2001/67382 | 2001-10-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1575272A true CN1575272A (en) | 2005-02-02 |
| CN1314655C CN1314655C (en) | 2007-05-09 |
Family
ID=19715557
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|---|---|---|---|
| CNB02820865XA Expired - Fee Related CN1314655C (en) | 2001-10-31 | 2002-06-21 | Method for preparing 4-nitroso-substituted aromatic amine |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US6552229B1 (en) |
| KR (1) | KR20030035343A (en) |
| CN (1) | CN1314655C (en) |
| AU (1) | AU2002314585A1 (en) |
| WO (1) | WO2003037831A2 (en) |
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| CN106699571A (en) * | 2016-11-16 | 2017-05-24 | 南京工业大学 | Preparation method of 2,5-dichloroaniline |
| CN112194584A (en) * | 2020-09-18 | 2021-01-08 | 江苏方圆芳纶研究院有限公司 | Method for preparing 4-nitrosoaniline and 4-nitroaniline |
| CN112209835A (en) * | 2020-09-18 | 2021-01-12 | 江苏方圆芳纶研究院有限公司 | Method for preparing p-phenylenediamine |
| CN113227041A (en) * | 2019-01-31 | 2021-08-06 | 组合化学工业株式会社 | Process for producing nitroso compound and quinoxaline compound |
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| CN106349084B (en) * | 2016-08-26 | 2018-08-07 | 安徽省虹升生物股份有限公司 | A kind of preparation method of the fluoro- 3- chloroanilines of 4- |
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| JPS5377026A (en) * | 1976-12-15 | 1978-07-08 | Nissan Chem Ind Ltd | Preparation of p-nitrosoaniline |
| US5117063A (en) * | 1991-06-21 | 1992-05-26 | Monsanto Company | Method of preparing 4-aminodiphenylamine |
| EP0566783A1 (en) * | 1992-04-21 | 1993-10-27 | Akzo N.V. | Process for the production of nitrodiarylamines |
| US5331099A (en) * | 1992-05-22 | 1994-07-19 | Monsanto Company | Process for preparing p-nitroaromatic amides and products thereof |
| US5380946A (en) | 1993-07-30 | 1995-01-10 | Monsanto Company | Process for preparing p-nitroaromatic amides and products thereof |
| DE4427248A1 (en) * | 1994-08-02 | 1996-02-08 | Bayer Ag | Process for the preparation of nitro-substituted arylamides and arylamines |
| DE4427249A1 (en) * | 1994-08-02 | 1996-02-08 | Bayer Ag | Process for the preparation of nitro-substituted arylamines |
| KR100294125B1 (en) * | 1999-11-16 | 2001-06-15 | 박찬구 | Manufacturing method for 4-Nitrosoaniline from Urea and Nitrobenzene |
| KR100362772B1 (en) * | 2000-07-07 | 2002-12-11 | 금호석유화학 주식회사 | A Novel Method of Preparing p-Phenylenediamine |
-
2001
- 2001-10-31 KR KR1020010067382A patent/KR20030035343A/en not_active Application Discontinuation
-
2002
- 2002-06-21 AU AU2002314585A patent/AU2002314585A1/en not_active Abandoned
- 2002-06-21 WO PCT/KR2002/001181 patent/WO2003037831A2/en not_active Application Discontinuation
- 2002-06-21 CN CNB02820865XA patent/CN1314655C/en not_active Expired - Fee Related
- 2002-07-31 US US10/209,263 patent/US6552229B1/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699571A (en) * | 2016-11-16 | 2017-05-24 | 南京工业大学 | Preparation method of 2,5-dichloroaniline |
| CN113227041A (en) * | 2019-01-31 | 2021-08-06 | 组合化学工业株式会社 | Process for producing nitroso compound and quinoxaline compound |
| CN113227041B (en) * | 2019-01-31 | 2023-03-24 | 组合化学工业株式会社 | Process for producing nitroso compound and quinoxaline compound |
| CN112194584A (en) * | 2020-09-18 | 2021-01-08 | 江苏方圆芳纶研究院有限公司 | Method for preparing 4-nitrosoaniline and 4-nitroaniline |
| CN112209835A (en) * | 2020-09-18 | 2021-01-12 | 江苏方圆芳纶研究院有限公司 | Method for preparing p-phenylenediamine |
| CN112194584B (en) * | 2020-09-18 | 2023-08-15 | 江苏方圆芳纶研究院有限公司 | Method for preparing 4-nitrosoaniline and 4-nitroaniline |
| CN112209835B (en) * | 2020-09-18 | 2023-10-27 | 江苏方圆芳纶研究院有限公司 | Method for preparing p-phenylenediamine |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20030035343A (en) | 2003-05-09 |
| CN1314655C (en) | 2007-05-09 |
| WO2003037831A2 (en) | 2003-05-08 |
| WO2003037831A3 (en) | 2003-11-20 |
| US6552229B1 (en) | 2003-04-22 |
| AU2002314585A1 (en) | 2003-05-12 |
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